Process for manufacturing titanium trichloride the catalysts obtained therefrom and their uses in the polymerization of polymerizable monomers

ABSTRACT

THE PRESENT DISCLOSURE IS DIRECTED TO A PROCESS FOR MANUFACTURING TITANIUM TRICHLORIDE BY REDUCING TITANIUM TETRACHLORIDE UTILIZING AT LEAST ONE REDUCING COMPOUND OF A METAL OF GROUPS I TO III, IN AND INERT SOLVENT. THE PROCESS IS CARRIED OUT IN TWO STEPS, THE FIRST STEP BEING CONDUCTED AT A TEMPERATURE LOWER THAN ABOUT 50*C. AND THE SECOND STEP BEING CONDUCTED AT A TEMPERATURE HIGHER THAN ABOUT 75*C. IN THE FIRST STEP, THE SOLVENT HAS A NORMAL BOILING POINT LOWER THAN 140*C. AND IN THE SECOND STEP THE SOLVENT HAS A NORMAL BOILING POINT HIGHER THAN 140*C.

United States Patent 3,640,987 PROCESS FOR MANUFACTURING TITANIUM TRICHLORIDE, THE CATALYSTS OBTAINED THEREFROM AND THEIR USES IN THE POLYMERIZATION 0F POLYMERIZABLE MONOMERS Nhu Hung Phung, Antony, and Gilles Le Febvre, La Celle St. Cloud, France, assignors to Institut Francais du Petrole des Carburants et Lubrifiants, Hauts-de- Seine, France No Drawing. Filed June 3, 1968, Ser. No. 804,722 Claims priority, application France, June I, 1967,

rm. or. cost 1/42, 3/10 US. Cl. 260-93.7 11 Claims ABSTRACT OF THE DISCLOSURE The present disclosure is directed to a process for manufacturing titanium trichloride by reducing titanium tetrachloride utilizing at least one reducing compound of a metal of Groups I to III, in an inert solvent. The process is carried out in two steps, the first step being conducted at a temperature lower than about 50 C. and the second step being conducted at a temperature higher than about 75 C. In the first step, the solvent has a normal boiling point lower than 140 C. and in the second step the solvent has a normal boiling point higher than 140 C.

This invention relates to the manufacture of a new type of catalyst exhibiting an increased activity, particularly for the stereospecific polymerization of ot-olefins. More particularly this invention relates to a new process for manufacturing highly efficient catalysts which may be used to polymerize propylene and its homologs to solid, highly crystalline polymers of high molecular weights.

It is well known to use catalysts in the stereospecifi'c polymerization, particularly that of a-olefins, said catalysts resulting from reacting compounds of transitional metals with organometal compounds.

Compounds of elements of Group IVa, Va or VIa of the Mendeleev chart are contacted with organometallic compounds or hydrides of metals, the metals in these compounds being chosen from the Groups I, II and III of the said chart.

The transition metal compound may be a halide, for example a titanium tetrachloride, whereas the organometallic compounds are most often organoaluminum compounds.

It is known to manufacture a catalytic system which is able to polymerize the ethylenic hydrocarbons to solid, highly crystalline polymers, by reducing a transition metal compound by means of an organometallic compound so as to constitute, after said reduction, a new compound of the transition metal. For example, titanium trichloride may be obtained by the reduction of titanium tetrachloride.

Titanium trichloride, such as obtained by these processes, is crystalline and exhibits a dark violet color; however, according to the manufacture process and the degree of purity, it exhibits a varying activity in the polymerization of a-olefins.

Several processes are known to obtain TiCl by the reduction of TiCl by means of organoaluminic compounds. Usually this reduction is carried out on dissolved TiCl using inert organic liquids (saturated aliphatic hydrocarbons such as heptane, decane, Vaseline oil, aromatic hydrocarbons such as benzene, xylene, aromatic compounds such as monochlorobenzene, ortho dichlorobenzene and the like).

It is also known to carry out the reduction of TiCl, in two steps corresponding to dilferent temperature ranges; in the first step, a solution of an organoaluminum compound in a hydrocarbon is added to a solution of TiCl in the same hydrocarbon, while the temperature is maintained below 50 C., for example between 30 and +30 C. Once the addition of the organoaluminic compound has come to an end, a second step follows by heating to a temperature higher than about C.

The resulting suspension is maintained at the second step temperature for, say, 1 to 6 hours, although these values are not limitative.

Usually this reduction of TiCl, is carried out either in a hydrocarbon solvent of high viscosity and boiling point, for example anhydrous Vaseline oil and decahydronaphthalene, and in that case the second step may be practiced at high temperature and atmospheric pressure, without any other change, or in a solvent of loW boiling point and reduced viscosity such as heptane, hexane, pentane or butane, the organoaluminic compounds having a higher reducing power in these solvents than in the high-boiling solvents. In this case, a second step follows at about 150 C., under superatmospheric pressure, which is of some trouble for the process.

The process which is an object of this invention makes possible to obtain by reduction of TiCl, with organoaluminic compounds, a product which exhibits improved catalytic properties.

According to this process, during a first step, titanium tetrachloride is reduced by means of a hydride or an organometallic compound whereof the metal is chosen from Group I, II or III, in a solvent of low, normal boiling point (for example lower than 140 C.) and consequently low viscosity, at temperatures lower than about 50 C. (preferably between 30 and +30 C.); this solvent of low boiling point is thereafter replaced by a solvent of high normal boiling point (preferably higher than 140 C.), for example by distillation or decantation, so as to continue the reduction, during the second step, in the presence of the said high boiling solvents, at a temperature higher than 75 C. The resulting product exhibits outstanding catalytic properties.

The catalytic activity of the thus obtained TiCl is higher than that of the product manufactured in one single solvent for the two steps.

According to this process, the first part of the reduction may be carried out in a solvent of low boiling point and viscosity, Whereas the second step may be carried out in a high boiling solvent at high temperatures, for example between and 200 C., preferably between and 180 C. at atmospheric pressure, although other pressures may be used.

As solvent of low boiling point, a saturated hydrocarbon of, for example, 4 to 8 carbon atoms per molecule will be preferred, for example, butane, hexane, heptane, octane, isooctane or cyclohexane, more particularly a solvent boiling normally between 0 and 100 C. As sol vent of high boiling point, a saturated hydrocarbon of 9 to 20 carbon atoms per molecule will be preferred, for example decahydronaphthalene, hexadecane, dodecane, Vaseline oil, more particularly a solvent of normal boiling point between and 250 C. Mixtures of these hydrocarbons may also be used.

This process makes possible not only to separate TiCl and the unreacted organoaluminic compounds, but also to improve the purity of TiCl (thus to improve its catalytic activity), by the elimination of the haloorganoaluminum compound resulting from the reaction.

As preferred reducing compounds, the following may be named: AlR RzRg, A1R1R2X1, A1R1X1X2 AlHR R or AlH R or aluminum hydrides also containing other elements such as alkali metals. R R and R are monovalent hydrocarbon radicals, for example alkyl, aryl, alkaryl, aralkyl, alkenyl, alkynyl, cycloalkyl and cycloalkenyl and X X and X, are identical or different halogen atoms, preferably Br or Cl. As a rule, it is possible to use all compounds containing at least one H- metal or C-metal bond, the metal being selected from those of Groups I to III of the Periodic Chart.

Heptane: 600 com. TiCl 0.9 g. Al(C2H5)2ClZ g. Temperature: 50 C. Pressure: 385 mm. Hg

After 5 hours, the polymerization is stopped by means of alcohol containing hydrochloric acid. The gaseous Preferably each of the R radicals contains 1 to 30 carbon atom propyleneis vaporlzed and, after cooling, the polymer is The reduction of TiCl, to TiCl is preferably carried washed W1t.h chimed ammoma' Fmany the resultmg poly out with atomic ratios Al/ Ti between 0.2 and 0.6. Propylene 1s dined tinder vacuum 78 polypropylene During the polymerization of propylene the use of are thus obtained, 1.e. an hourly production of 17 g. of trialkylaluminum as activator makes possible to obtain 20 Polymer Per gram 9 very high reaction rates, however difficult to control, and The conten? of lsotactlc Polymer 15 as determmed the obtained polymers have a low isotactic content. It is from the resldue of an extractlon Wlth heptane for 24 then usually preferable to activate titanium trichloride hours by means of compounds of general formula AIR R X so EMMPLE 2 as to obtain a high content of isotactic polymer and a TiCl is manufactured by the process described in Exgreat catalytic activity. ample 1, except that the first step temperature (reduction It has been surprisingly discovered that, for polymof TiCl by AI(C H is 10 C. erizing propylene, titanium trichloride, such as prepared Propylene is polymerized as described in Example 1, according to this invention, and activated by AlR R X however With the catalyst of Example 2, and similar rehas an outstanding catalytic activity (as measured, for suits are obtained, example, in grams of polymer per gram of TiCl and per EXAMPLE 3 hour of reaction) TiCl is manufactured with the same method and under great catalytlc actlglty also fi to S F the same conditions as in Examples 1 and 2 except that en.zatlon. temperatqre. i Pressure W 1 e O tammg Su the temperature in the reaction step Where TiCl is reduced ficient ylelds, to diminish the amount of catalyst to be by 5)3 20 C used for the i and to 5 -g g Propylene is polymerized in the same conditions as veryl p q W 16 18 more eas y Pun e romt 6 those of Examples 1 and 2. The results are given in ing: $1 1 b described hereafter the process of manu- 40 Table EXAMPLES 4 AND 4a facture of TiCl and the results of a given number of polymerization trials which are given by way of examples. By way of comparison, TiCl is manufactured with Examples 4 and 5 are given by way of comparison and heptane as sole solvent for the two steps of the reaction. form no part of this invention. The concentrations of reactants and the reaction temperature are the same as in Example 1. The second step EXAMPLE 1 is also carried out under a pressure which is close to the Manufacture of titanium trichloride P P 0f p The obtained TiCl is subjected to the same washing Into a reaction vessel of 1 liter capacity, is fit treatments as described in Example 1. with a stirrer of 200 rotations per minute and a cooler, 130 cm. of a solution are introduced which contain 0.18 EXAMPLE 5 AND 5a mole of titanium tetrachloride in heptane. This solution There is used decahydronaphthalene as solvent during is kept at 0 C. under stirring and 123 cm. of a solution the reduction of TiC1 by means of Al(C H This of 0.099 mole of Al(C H in heptane are introduced solvent exhibits a somewhat higher viscosity and boiling therein in the course of 45 minutes. The vessel which con- H point. tained Al(C H is rinsed with 10 cm. of heptane which This solvent is retained as hydrocarbon medium for are thereafter introduced into the reaction vessel. The the second step (heating to 150 0.). molar ratio of Al(C H to TiCl is 0.55. The concentration of the reactants and the reaction The resulting mixture is thereafter heated up to 150 C. temperature are as described in Example 1. The obtained in the course of 45 minutes. During the heating from 0 material is .washed with heptane and suspended in the to 150 C., heptane is removed by distillation. The dissame. tilled heptane is progressively replaced by the same vol- The resulting TiCl as Well as those of the previous ume of decahydronaphthalene before the temperature has examples, have given the following results (Table 1).

TABLE I Grams oflsotac- '1emp., Pressure, 'llmo, Activity, tieity Intrinsic A1(C2H5)2Ci 0.) mm. Hg. hours gJg. Ti/ii. percent viscosity 3. 72 50 385 5 17 5.5 a. 72 50 385 5 15.6 93 5. s 3. 72 50 335 5 13.8 94 6 3. 72 50 395 5 1a 87 4 a. 72 50 385 5 12 88 as 5 50 400 5 9.4 89 3.5 0 50 385 5 9.05 88 as 1 At C. in tetraiiydrouaphthaleue.

EXAMPLE 6 ganometallic compound selected from the group consist- TiCl is manufactured as described in Example 1, exmg of AlHs, 1 2 AlR R X AlR X X cept that pentane 1s used mstead of heptane. AIZRIRZRSXIXzX3 Propylene 1s polymerized with this catalyst under the conditions of Example 1. 5 1( 2) 3) 1) 2 1 2( 3),

After 5 hours, 65 g. of polymer are obtained whereof AIHR 1R2 the isotacticity is 90% and the intrinsic viscosity (1;) is 5.5 (as determined at 135 C. in tetrahydronaphthalene). 3 L 2 nd f i 1 2 a ei are monogalent yrocar on ra ica s containing mm to 30 car on atoms EXAMPLES 7 T016 and X X and X are identical or different halogens, at TiCl is manufactured as described in Example 1, how- 10 a temperature of about 30 to +30 C. in the presence ever with some changes. The conditions other than those of a low boiling saturated hydrocarbon solvent having a of Example 1 are giveninTable II. boiling point between about 0 and 100 C., progressively TABLE 11.

Temperature 0.)

Example 1st step solvent Reducing agent 1st step 2d step 2d step solvent 7 Hexane AlOl(C2H5)2 0 150 Deeahydronaphthalene. Octane AlCl2C2H5 10 160 Hexadecane. Cyelohexan Al2Cla(C2H' )3 0 160 Do.

Butane AlBr(C H )1 0 120 Dodecane 1Ieptane Zn(CzH5)2 0 140 0- 12 Pentane MUG/H3); 10 180 Vaseline oil. 13 Heptane MgBICaHs 160 o. I 14 do AlH(CzH5)2 0 150 Mlxture of hexadecane with dodecane by equal volumes. 15 do All-1202115 0 150 D0. 16 do AI(OC2H5)2C2H5 0 150 Decahydronaphthalene.

Propylene is thereafter polymerized under the conditions of Example 1 with each of the TiCl obtained in Examples 7 to 16. The results are substantially the same as in Example 1.

What is claimed is:

1. A process for producing titanium trichloride by the reduction of titanium tetrachloride which comprises reducing titanium tetrachloride in a first stage with an organometallic compound selected from the group consisting of A1H3, AlR RzRg, A1R1R2X1, A1R1X1X2, 2 1 2 s 1 2 s 1( 2)( 3) 1) 2 AlR R (OR AlHR R and AlH R wherein R R and R are monovalent hydrocarbon radicals containing from 1 to carbon atoms and X X and X are identical or dilferent halogens, at a temperature of about 30 to +30 C. in the presence of a low boiling saturated hydrocarbon solvent or a mixture of low boiling saturated hydrocarbon solvents having about 4 to 8 carbon atoms, and boiling at a temperature between about 0 to 100 C., replacing said low boiling solvent with a high boiling saturated hydrocarbon solvent or a mixture of high boiling saturated hydrocarbon solvents having about 9 to 20 carbon atoms and boiling at a temperature between about 150 to 250 C. and continuing the reduction in a second stage at a temperature of about 100 to 200 C. in the presence of said high boiling solvent.

2. The process of claim 1, wherein the second stage is conducted at a temperature of 140 to 180 C.

3. The process of claim 1, wherein the atomic ratio of Al/Ti of the aluminum compounds to the titanium tetrachloride is between about 0.2 and 0.6.

4. The process of claim 1, wherein the first stage solvent is progressively replaced by the second stage solvent during the removal of the first solvent.

5. The process of claim 1, wherein the organometallic compound is selected from the group consisting of 6. A process for producing titanium trichloride by the reduction of titanium tetrachloride which comprises reducing titanium tetrachloride in a first stage with an orremoving the low boiling solvent during a second stage by distillation and replacing it with a high boiling saturated hydrocarbon solvent having a boiling point between about 150 and 250 C. and continuing the reduction in said second stage at a temperature of about to 200 C. in the presence of said high 'boiling solvent.

7. The process of claim 6, wherein the atomic ratio Al/Ti of the aluminum compounds to the titanium tetrachloride is between about 0.2 and 0.6.

8. A process for polymerizing u-olefinic hydrocarbons which comprises contacting said olefinic hydrocarbons with a titanium trichloride catalyst produced by reducing titanium tetrachloride in a first stage with an organometallic compound selected from the group consisting of AlH AlR RgRg, AIR1R2X1, A1R1X1X2,

and AIH R wherein R R and R are monovalent hydrocarbon radicals containing from 1 to 30 carbon atoms and X and X and X, are identical or different halogens, at a temperature of about 30 to +30 C. in the presence of a low boiling saturated hydrocarbon solvent or a mixture of low boiling saturated hydrocarbon solvents having about 4 to 8 carbon atoms, and boiling at a temperature between about 0 to 100 C., replacing said low boiling solvent with a high boiling saturated hydrocarbon solvent or a mixture of high boiling saturated hydrocarbon solvents having about 9 to 20 carbon atoms and boiling at a temperature between about and 250 C. and continuing the reduction in a second stage at a temperature of about 100 to 200 C. in the presence of said high boiling solvent, said catalyst being activated with an organometallic compound of the formula where R and R are monovalent hydrocarbon radicals and X is a halogen atom.

9. The process of claim 8, wherein the a-olefinic hydrocarbon is propylene.

10. A process for polymerizing tit-olefinic hydrocarbons which comprises contacting said olefinic hydrocarbons with a titanium trichloride catalyst produced by reducing titanium tetrachloride in a first stage with an organometallic compound selected from the group consisting of AIH3, A1R1R2R3, A1R1R2X1, AIRIXIXZ, A12R1R2R3X1X2X3: 1( z)( 3) 1) 2 AlR R (OR AlI-IR R and AlH R wherein R R and R are monovalent hydrocarbon radicals containing from 1 to 30 carbon atoms and X X and X; are identical or different halogens, at a temperature of about 30 to +30 C. in the presence of a low boiling saturated hydrocarbon solvent having a boiling point between about 0 and 100 C., progressively removing the low boiling solvent during a second stage by distillation and replacing it With a high boiling saturated hydrocarbon solvent having a boiling point between about 150 and 250 C. and continuing the reduction in said second stage at a temperature of about 100 to 200 C. in the presence of said high boiling solvent, said catalyst being activated with an organometallic compound of the formula A1R R X where R and R are monovalent hydrocarbon radicals and X is a halogen atom.

11. The process of claim 10, wherein the organometallic compound used to activate said titanium trichloride catalyst is Al(C H C1.

References Cited UNITED STATES PATENTS JOSEPH L. SCHOFER, Primary Examiner E. J. SMITH, Assistant Examiner U.S. C1. X.R. 

